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A photoswitchable polar crystal that exhibits superionic conduction

Nature Chemistry volume 12, pages 338–344 (2020)Cite this article

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Abstract

Ionic conductors serve as solid electrolytes for fuel cells and batteries, whereas polar crystals such as ferroelectrics and pyroelectrics—which are typically insulating materials—are used in electronic devices. Here we show a material that combines superionic conductivity with a polar crystal structure at room temperature. This three-dimensional anionic network is based on –Fe–N≡C–Mo– units, with Cs cations hosted in every other pore. In the resulting Cs1.1Fe0.95[Mo(CN)5(NO)]·4H2O material, the negative and positive charges of the framework and Cs+ ions, respectively, are non-symmetrically shifted in the c-axis direction of the unit cell, and spontaneous electric polarization is generated, in turn leading to second harmonic generation (SHG). Additionally, this material is a superionic conductor (with an ionic conductivity value of 4 × 10−3 S cm−1 at 318 K). Furthermore, the ionic conductivity significantly decreases under 532 nm light irradiation (from 1 × 10−3 S cm−1 to 6 × 10−5 S cm−1 at room temperature) and, when irradiation stops, returns to its original value within ~1 h.

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Fig. 1: Synthesis and crystal structure of CsFeMo.
Fig. 2: Characterization of the spectroscopic properties of CsFeMo.
Fig. 3: Superionic conductivity in CsFeMo.
Fig. 4: Optical switching of the ionic conductivity of CsFeMo.

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Data availability

X-ray crystallographic data have been deposited at the Cambridge Crystallographic Data Centre (http://www.ccdc.cam.ac.uk/) with reference no. 1907012. A copy of the data can be obtained free of charge via https://www.ccdc.cam.ac.uk/structures/. All other data supporting the findings of this study are available within the Article and its Supplementary Information. Data are also available from the corresponding author upon reasonable request.

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Acknowledgements

The present research was supported partly by a JSPS Grant-in-Aid for Specially Promoted Research (grant 15H05697). We also recognize the Cryogenic Research Center, The University of Tokyo and the Center for Nano Lithography & Analysis, The University of Tokyo, which are supported by MEXT. We thank M. Komura, M. Numanyu and T. Chiba of Olympus Corporation for the SHG microscopy imaging.

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Authors and Affiliations

  1. Department of Chemistry, School of Science, The University of Tokyo, Bunkyo-ku, Tokyo, Japan

    Shin-ichi Ohkoshi, Kosuke Nakagawa, Kenta Imoto, Hiroko Tokoro, Yuya Shibata, Kohei Okamoto, Yasuto Miyamoto, Masaya Komine, Marie Yoshikiyo & Asuka Namai

  2. Division of Materials Science, Faculty of Pure and Applied Sciences, University of Tsukuba, Tsukuba, Ibaraki, Japan

    Hiroko Tokoro

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Contributions

S.O. designed and coordinated this study, contributed to all measurements and analyses, and wrote the paper. K.N. conducted the conductivity measurements. K.I. conducted the 57Fe Mössbauer spectrum measurements and conductivity measurements. H.T. contributed to the setup of the conductivity measurements and IR measurement systems. Y.S. contributed to the sample characterization, SHG and THz-TDS measurements. K.O. contributed to the sample preparation and TG measurements. Y.M. contributed to the crystal structure analysis. M.K. contributed to the IR measurements. M.Y. contributed to SEM and optical microscopy imaging and partially wrote the paper. A.N. contributed to the analyses of crystal structure and IR spectra, and helped prepare the figures.

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Correspondence to Shin-ichi Ohkoshi.

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Supplementary information

Supplementary Information

Supplementary Video 1, SEM image and size distribution, crystal structure analysis, terahertz-time domain spectrum, magnetic properties, SHG measurements, photoswitching effect of ionic conductivity, and differential infrared spectra before and after light irradiation.

Crystallographic data

Crystallographic Information File for CsFeMo, CCDC 1907012

Crystallographic data

Structure factors for CsFeMo, CCDC 1907012

Supplementary Video 1

Polar crystal exhibiting a superionic conductivity and optical-switching effect

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Ohkoshi, Si., Nakagawa, K., Imoto, K. et al. A photoswitchable polar crystal that exhibits superionic conduction. Nat. Chem. 12, 338–344 (2020). https://doi.org/10.1038/s41557-020-0427-2

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